Bichromophoric benzoxazole-styrene ester and amide ultraviolet stabilizers and their use in organic compositions

ABSTRACT

The invention relates to bichromophoric benzoxazole-styrene ester and amide compounds which have been found to be effective ultraviolet stabilizers. The invention also relates to ultraviolet degradable organic compositions containing a stabilizing amount of the bichromophoric composition to prevent such degradation. These stabilizers are effective in the presence of other additives commonly employed in polymeric compositions including, for example, pigments, colorants, fillers, reinforcing agents and the like. These ultraviolet stabilizers may also be incorporated into the organic compositions in the polymer melt or dissolved in the polymer dope, coated on the exterior of the molded article, film or extruded fiber.

This application is a divisional application of Ser. No. 714,927, filed Aug. 16, 1976, now U.S. Pat. No. 4,062,800.

This invention relates to bichromophoric ultraviolet stabilizers and their use in organic compositions. More particularly, the invention relates to bichromophoric compositions and the stabilization of ultraviolet degradable organic compositions against deterioration resulting from the exposure to such radiations with such bichromophoric compositions.

The degradative effects of ultraviolet light on various organic compositions is well known in the art. The photo-deterioration or degradation is of particular concern with organic photo-degradable compositions which are exposed to ultraviolet light, such as sunlight, for long periods of time. One group of such photo-degradable organic compositions is polymeric compositions such as polyolefins, polyesters and the like. On exposure to sunlight for extended periods of time, these polymeric compositions degrade and their physical properties are reduced to render the polymeric composition less useful for most applications. Therefore, considerable effort has been directed to providing a solution to the photo-degradation problem of polymeric compositions. As a result of this effort, there have been discovered many additives and stabilizers which improve the stability of polymeric compositions.

Moreover, various additives and stabilizers exhibit the power to absorb ultraviolet radiation within the band of 2900 to 4000 A. and, when incorporated in various plastic materials such as transparent sheets, the resultant sheet acts as a filter for all the radiation passing through and will transmit only such radiations as are not absorbed by the sheet and/or the absorbing agent. It is thus possible to screen out undesirable radiations and utilize the resulting transparent sheet as a filter in many technical and commercial applications, such as wrappings for food products and the like.

While there are many additives, stabilizers and mixtures thereof which are known in the art to improve the ultraviolet light stability of organic compositions, there is a need in the art for more efficient and effective stabilizers to prevent the photo-degradation of organic compositions susceptible to photo-degradation. Therefore, to provide a more effective and efficient ultraviolet stabilizer for organic compositions susceptible to such degradation would be an advance in the state of the art.

It is, therefore, an object of the present invention to provide more effective and efficient ultraviolet light stabilizer compositions.

Another object of the present invention is to provide useful compositions characterized by improved resistance to ultraviolet degradation and deterioration.

It is still another object of the present invention to provide compositions containing bichromophoric compositions which are resistant to ultraviolet degradation.

It is a still further object of this invention to provide processes for improving the resistance of organic materials to deterioration and degradation by actinic radiation and especially ultraviolet radiation.

It is a still further object of this invention to provide compositions and processes for improving the resistance of organic materials to deterioration and degradation by actinic radiations, including short wave-length visible radiations.

Further objects and advantages of the invention will be apparent to those skilled in the art from the accompanying disclosure and claims.

In accordance with the present invention, bichromophoric compositions are provided which are useful as ultraviolet stabilizers or ultraviolet screening agents. These organic compositions contain at least one benzoxazole heterocyclic group containing composition connected to a styrene group. The bichromophoric compositions of the present invention have the following structure:

    A--B--C

wherein A is a group having the structure ##STR1## wherein

R₁, R₂, R₃ and R₄ are hydrogen, lower alkyl or substituted lower alkyl having 1 to 12 carbon atoms, cycloalkyl, substituted cycloalkyl, aryl or substituted aryl having 6 to 18 carbon atoms, lower alkylaryl, aryl-substituted-aryl, chloro, bromo, alkoxy, substituted amino, cyano, carboalkoxy and the substituents R₁ and R₂, R₂ and R₃, and R₃ and R₄, combined with the carbon atoms to which they are attached, are joined alkylene groups completing a carbocyclic ring, which ring can also be substituted with one or more of the substituents listed above for R₁, R₂, R₃ and R₄.

I is a substituent listed above for R₁, R₂, R₃ and R₄ and is present on all positions of the benzenoid ring, except the carbon atom attached to the oxazole ring and the carbon atom attached to the B group. The B connecting group is attached to the benzenoid ring in the ortho, meta or para position from the carbon atom connected to the oxazole heterocyclic ring. The I substituents can all be one of the substituents listed above or different listed substituents;

wherein B is a linking group connecting A and C and can be oxy, oxycarbonylalkyleneoxy, alkyleneoxy, alkyleneoxyalkyleneoxy, oxyalkylenearylenealkyleneoxy, thio, thioalkyleneoxy, sulfinyldioxy, oxy(alkoxy)phosphinooxy, aminocarbonylalkyleneoxy, N-alkylaminocarbonylalkyleneoxy, N-arylaminocarbonylalkyleneoxy, aminocarbonylamino, N-alkylaminocarbonylamino, amino, N-alkylamino, N-arylamino, N-alkylaminoalkyleneoxy, N-arylaminoalkyleneoxy, oxyalkyleneoxy, oxyaryleneoxy, alkyleneaminoalkylene, aryleneaminoarylene, aryleneaminoalkylene and alkyleneaminoarylene; and

C is a group having the formula ##STR2## where I is the same substituent as listed above and said I substituents can all be one of the substituents listed above or different listed substituents and R₅ is an alkyl group containing 1 to 20 carbon atoms and R₆ is cyano, alkylsulfonyl, arylsulfonyl, arylcarbonyl, alkylcarbonyl or carbonylalkoxy. The B connecting group is attached to the benzenoid ring the the ortho, meta or para position from the nitrogen group of the oxazole ring.

Suitable heterocyclic A groups having the structure ##STR3## are for example substituted and unsubstituted 2-phenylbenzoxazoles, such as 4-(2-benzoxazolyl)phenyl, 2-chloro-4-(2-benzoxazolyl)phenyl, 2-methyl-4-(5,6-dimethyl-2-benzoxazolyl)phenyl, 4-(5,6-dimethyl-2-benzoxazolyl)phenyl, 4-(5-chloro-2-benzoxazolyl)phenyl, 4-(5-methyl-2-benzoxazolyl)phenyl, 4-(5-cyano-2-benzoxazolyl)phenyl, 4-(5-bromo-2-benzoxazolyl)phenyl, 3-chloro-4-(5,6-dimethyl-2-benzoxazolyl)phenyl, 4-(5-cyclohexyl-2-benzoxazolyl)phenyl, 2-(2-benzoxazolyl)phenyl, 4-chloro-2-(2-benzoxazolyl)phenyl, 3-(2-benzoxazolyl)phenyl, 4-chloro-3-(2-benzoxazolyl)phenyl, 2-chloro-3-(2-benzoxazolyl)phenyl, 2-methyl-3-(5,6-dimethyl-2-benzoxazolyl)phenyl, 3-(5,6-dimethyl-2-benzoxazolyl)phenyl, 3-(5-chloro-2-benzoxazolyl)phenyl, 3-(5-methyl-2-benzoxazolyl)phenyl, 3-(5-cyano-2-benzoxazolyl)phenyl, 3-(5-bromo-2-benzoxazolyl)phenyl, 6-chloro-3-(5,6-dimethyl-2-benzoxazolyl)phenyl, 3-(5-cyclohexyl-2-benzoxazolyl)phenyl, and the like.

Suitable B groups are for example oxy, oxycarbonylmethyleneoxy, oxycarbonylethyleneoxy, oxycarbonyl-1,4-butanediyloxy, alkyleneoxy such as methyleneoxy, ethyleneoxy, 1,3-propanediyloxy and the like, alkyleneoxyalkyleneoxy such as methyleneoxymethyleneoxy, ethyleneoxyethyleneoxy, methyleneoxyethyleneoxy, ethyleneoxymethyleneoxy and the like, oxyalkyleneoxy such as oxymethyleneoxy, oxyethyleneoxy, oxy-1,4-butanediyloxy and the like, oxyalkylenearylenealkyleneoxy such as oxymethylenephenylenemethyleneoxy, oxyethylenephenylenemethyleneoxy, oxypropylenephenylenemethyleneoxy, oxyethylenenaphthyleneethyleneoxy and the like, thio, thioalkyleneoxy such as thioethyleneoxy and the like, aminocarbonyl, N-alkylaminocarbonyl such as N-methylaminocarbonyl, N-ethylaminocarbony, N-butylaminocarbonyl and the like, N-arylaminocarbonyl such as N-phenylaminocarbonyl, N-(3-methylphenyl)aminocarbonyl and the like, aminocarbonylalkyleneoxy such as aminocarbonylmethyleneoxy, aminocarbonyl-1,4-butanediyloxy, N-methylaminocarbonylmethyleneoxy, N-phenylaminocarbonylethyleneoxy and the like, aminocarbonylamino, alkylaminocarbonylamino such as N-methylaminocarbonylamino, N-ethyaminocarbonylamino and the like, di(N-alkylamino)carbonyl such as N-methylaminocarbonyl-N'-methylamino, N-ethylaminocarbonyl-N'-methylamino, N-ethylaminocarbonyl-N'-butylamino and the like, arylaminocarbonylamino such as N-phenylaminocarbonylamino, N-(3-methylphenyl)aminocarbonylamino, N-arylaminocarbonyl-N'-arylamino, such as N-phenylaminocarbonyl-N'-phenylamino, N-alkylaminocarbonyl-N'-arylamino such as N-methylaminocarbonyl-N'-phenylamino and the like, N-arylaminocarbonyl-N'-alkylamino such as N-phenylaminocarbonyl-N'-methylamino or N-methylaminocarbonyl-N'-phenylamino and the like, amino, alkyleneamino such as methyleneamino, 1,4-butanediylamino, 1,5-pentanediylamino, and the like, aryleneamino such as phenyleneamino and the like, N-alkylaminoalkyleneoxy such as N-methylaminomethyleneoxy, N-ethylaminomethyleneoxy and the like, N-arylaminoalkyleneoxy such as N-phenylaminomethyleneoxy, N-phenylaminoethyleneoxy and the like, oxyalkyleneaminoalkyleneoxy such as oxymethyleneaminomethyleneoxy, oxymethyleneaminoethyleneoxy and the like, alkyleneaminocarbonylamino such as methyleneaminocarbonylamino, ethyleneaminocarbonylamino and the like, oxyalkylene(N-alkyl)aminoalkyleneoxy such as oxymethylene(N-methyl)aminomethyleneoxy and the like.

wherein C is a styrene group having the formula ##STR4## are for example 2-(4-methoxyphenyl)-1-cyanoacryloyl, 2-(2-methyl-4-n-butoxyphenyl)-1-cyanoacryloyl, 2-(2,5-dimethyl-4-isooctyloxyphenyl)-1-cyanoacryloyl, 2-(2-chloro-4-ethoxyphenyl)-1-cyanoacryloyl, 2-(2-butamido-4-n-butoxyphenyl)-1-cyanoacryloyl, 2-(2-cyano-4-methoxyphenyl)-1-cyanoacryloyl, 2-(2-ethoxy-4-ethoxyphenyl)-1-cyanoacryloyl, 2-(2,5-dichloro-4-cyclohexyloxyphenyl)-1-cyanoacryloyl, 2-(4-n-octadecyloxyphenyl)-1-cyanoacryloyl, 2-(4-isopropyloxyphenyl)-1-cyanoacryloyl, 2-(4-methoxyphenyl)-1-methylsulfonylacryloyl, 2-(4-methoxyphenyl)-1-benzoylacryloyl, 2-(4-methoxyphenyl)-1-propionylacryloyl, 2-(4-methoxyphenyl)-1-benzenesulfonylacryloyl, 2-(2-methyl-4-methoxyphenyl)-1-cyanoacryloyl, 2-(2-chloro-4-methoxyphenyl)-1-p-toluenesulfonylacryloyl.

The bichromophoric composition can be added to organic compositions which are susceptible to ultraviolet degradation. Such compositions include, for example, polymeric compositions such as polyester fiber and molding compositions, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate) and the like; polyolefins such as, for example, high, medium and low density polyethylene, polypropylene, polybutene and the like; polyamides such as N-methoxymethyl polyhexamethylene adipamide and the like; polycarbonates; polyvinyl chlorides and copolymers; cellulose esters; acrylic/butadiene/styrene plastic; polyacrylics such as methyl methacrylate; polystyrene; gelatin; fluorocarbon polymers such as poly(vinylidene fluoride); vinylidene chloride copolymers such as vinylidene chloride/vinyl acetate copolymers; ethylene vinyl acetate copolymers; cellulose ethers such as methyl cellulose; polyvinyl esters such as polyvinyl acetate; polyethylene oxide; polyvinyl acetals; polyformaldehydes; and polyurethanes. Such compositions also include natural and synthetic rubbers, such as polybutadiene, and unsaturated organic compositions such as oils and the like, as well as compositions containing such organic compositions.

The bichromophoric compositions, as effective ultraviolet stabilizers or screening agents, are generally used in an amount of from 0.01 to 10%, by weight, based on the weight of the organic material to which they are added. While a detectable amount of ultraviolet screening and stabilization may be obtained with amounts less than 0.01%, this amount of stabilization or screening would be of little practical utility in a commercial application. Moreover, while amounts greater than 10%, by weight, provide effective ultraviolet stability and screening, such concentrations are undesirable because of cost and the deleterious effect which such concentrations may have on the mechanical properties of the organic composition in which the stabilizer is incorporated. Preferably, the stabilizer is used in an amount of from about 0.1 to about 3%, by weight. For example, an amount of 2%, by weight, of the stabilizer effectively stabilizes cellulose acetate butyrate plastic compositions.

The ultraviolet stabilized organic compositions of the present invention may also contain other additives, pigments, colorants, stabilizers and the like. For example, polymeric compositions, such as polyolefins, may also contain and generally do contain other additives such as white or colored pigments or colorants, antioxidants, plasticizers, flow aids, processing aids, polymeric modifiers and the like.

These novel bichromophoric ultraviolet stabilizers may be incorporated into organic compositions by melt-blending or may be added onto the surface of an organic plastic material prior to being molded into a suitable object. These materials can also be added to coatings and the like which can be applied to the surface of a molded object.

This invention will be further illustrated by the following example although it will be understood that this example is included merely for purposes of illustration and is not intended to limit the scope of the invention.

EXAMPLE 1

Preparation of 4-(2-benzoxazolyl)benzyl 2-cyano-3-(4-methoxyphenyl)acrylate (I).

Cyanoacetyl chloride (0.1 mole) was added in 30 minutes to a solution of 0.1 mole 2-(4-hydroxymethylphenyl)benzoxazole (A) in 300 ml. methylene chloride containing 10 g. potassium carbonate. After stirring at 25° C. for 15 hours, the mixture was filtered and evaporated to dryness. Crude B was recrystallized from methyl cellosolve/isopropyl alcohol to yield pure B (62%). B (0.1 mole) and 4-methoxybenzaldehyde (0.1 mole) in 300 ml. 1,2-dimethoxyethane containing a trace of pyridine/piperidine was stirred for 15 hours, and cooled to precipitate I. Recrystallization from toluene provided a 47% yield of tan, crystalline I. ##STR5##

Other novel bichromophoric compounds can be prepared by substitution of other benzoxazoles for A, such as: 4-(5,6-dichloro-2-benzoxazolyl)benzyl alcohol, 4-(5-chloro-2-benzoxazolyl)benzyl alcohol, 4-(5-cyano-2-benzoxazolyl)benzyl alcohol, 4-(5,6-dimethyl-2-benzoxazolyl)benzyl alcohol, 4-(5-methyl-2-benzoxazolyl)benzyl alcohol, 4-(5-cyclohexyl-2-benzoxazolyl)benzyl alcohol, 4-(5-t-butyl-2-benzoxazolyl)phenyl ethanol, 4-(5-methoxy-2-benzoxazolyl)benzyl amine, 4-(2-benzoxazolyl)-2-chlorophenol, 4-(2-benzoxazolyl)-2,5-dichlorothiophenol, 4-(2-benzoxazolyl)-2-methylaniline, 3-(2-benzoxazolyl)benzyl alcohol, 3-(5-chloro-2-benzoxazolyl)phenol, 3-(5-cyano-2-benzoxqzolyl)phenoxyethanol, 3-(5-methylthio-2-benzoxazolyl)phenylethylamine, 3-(5-n-butoxy-2-benzoxazolyl)benzyl alcohol, 3-(5-cyclopentyl-2-benzoxazolyl)benzyl alcohol, 3-(5,6-dimethyl-2-benzoxazolyl)benzyl alcohol, 3-(5,6-dichloro-2-benzoxazolyl)benzyl alcohol, and the like.

Also, other bichromophoric compounds can be prepared by substituting other acid chlorides for cyanoacetyl chloride, such as methanesulfonylacetyl chloride, ethanesulfonylacetyl chloride, cyclohexanesulfonylacetyl chloride, carbo-t-butoxyacetyl chloride, acetoacetyl chloride, benzoylacetyl chloride, 1-(4-chlorobenzoyl)acetyl chloride and the like; or by substituting other aldehydes for 4-methoxybenzaldehyde, such as 2-methyl-4-methoxybenzaldehyde, 4-(n-dodecyloxy)benzaldehyde, 2,4-dimethylbenzaldehyde, 2,6-dichloro-4-methoxybenzaldehyde, 2-chloro-4-benzyloxybenzaldehyde, 2-methyl-4-(β-methoxyethoxy)benzaldehyde, 4-cyclohexyloxybenzaldehyde. Moreover, while the example illustrates a sequence of reactions in which the final step involves reaction of an aldehyde with an "active methylene" compound B, alternative syntheses are often preferred, and are, in fact, well known in the art. For instance, the preparation of I could have involved reaction of the benzoxazole A with the acid chloride C. ##STR6##

The example hereinabove shows the linking group as a methyleneoxy group. Other linking groups can be provided as known in the art, as for example:

1. an oxycarbonylalkyleneoxy by esterification of an acid or acid chloride with an alcohol or phenol in alkaline medium;

2. an oxycarbonyloxy by the reaction of phosgene with alcohol or phenol in alkaline medium;

3. an oxy by the reaction of an acid chloride with alkali salt of a phenol;

4. an alkyleneoxyalkyleneoxy by the reaction of halide with alkali salt of alcohol or phenol;

5. a sulfinyldioxy by the reaction of thionyl chloride with alcohol or phenol in alkaline solution;

6. a thio by the reaction of a sodium sulfide with a halide;

7. an oxy(alkoxy)phosphinooxy by the reaction of a dichlorophosphite with phenol in the presence of a base;

8. an N-alkyl or N-arylaminocarbonyl by the reaction of an acid chloride with an amine;

9. an N-alkyl or N-arylaminocarbonylalkoxy by the reaction of an acid chloride with an amine;

10. an N-alkyl or N-arylaminocarbonylamino by the reaction of phosgene with an amine;

11. an N-alkyl or N-arylaminoalkylene by the reaction of an alkyl halide with an amine;

12. an N-alkyl or N-arylaminoalkyleneoxy by the reaction of an oxyalkyl halide with an amine.

These bichromophoric compositions find particle utility as ultraviolet stabilizers in organic compositions requiring ultraviolet stability. Such compositions include polymeric compositions such as, for example, polyester fiber and molding compositions, poly-alpha-olefins, polyamides, acrylics, cellulose esters and the like, as well as molded or shaped articles, film and coatings formed from such materials and the like. Such compositions also include natural and synthetic rubbers, such as natural rubber, as well as organic materials such as oils, fats, and unsaturated organic materials and materials having such materials contained therein such as paints, varnishes, cosmetics and the like.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula:

    A--B--C

wherein A is a group having the structure ##STR7## wherein R₁, R₂, R₃ and R₄ are hydrogen, chloro, bromo, lower alkyl, substituted lower alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, lower alkylaryl, aryl-substituted-aryl, alkoxy, substituted amino, cyano, carboalkoxy and the substituents R₁ and R₂, R₂ and R₃, and R₃ and R₄, combined with the carbon atoms to which they are attached, are joined alkylene groups completing a carbocyclic ring, which ring can also be substituted with one or more of the substituents listed above for R₁, R₂, R₃ and R₄ ; I is the same as R₁, R₂, R₃ and R₄ and is present on all positions of the benzenoid ring, except the carbon atom attached to the heterocyclic ring and the carbon atom attached to the B group connecting the heterocyclic aromatic A group with the aromatic C group, wherein B is a linking group connecting A and C and can be oxy, oxycarbonylalkyleneoxy, alkyleneoxy, alkyleneoxyalkyleneoxy, oxyalkylenearylenealkyleneoxy, thio, thioalkyleneoxy, aminocarbonylalkyleneoxy, N-alkylaminocarbonylalkyleneoxy, N-arylaminocarbonylalkyleneoxy, N-alkylamino, N-arylamino, N-arylaminoalkyleneoxy, N-alkyleneaminoalkyleneoxy, oxyalkyleneoxy, oxyaryleneoxy; and wherein C is a group having the formula ##STR8## where I is the same substituent as listed above and said I substituents can all be one of the substituents listed above or different listed substituents and R₅ is an alkyl group containing 1 to 20 carbon atoms and R₆ is cyano, carboxamido, alkanoyl or alkylsulfonyl.
 2. A compound according to claim 1 wherein said B linking group is oxycarbonylalkyleneoxy.
 3. A compound according to claim 1 wherein said B linking group is alkyleneoxy.
 4. A compound according to claim 1 wherein said B linking group is alkyleneoxyalkyleneoxy.
 5. A compound according to claim 1 wherein said B linking group is oxyalkylenearylenealkyleneoxy.
 6. A compound according to claim 1 wherein said B linking group is thio.
 7. A compound according to claim 1 wherein said B linking group is thioalkyleneoxy.
 8. A compound according to claim 1 wherein said B linking group is aminocarbonylalkyleneoxy.
 9. A compound according to claim 1 wherein said B linking group is N-alkylaminocarbonylalkyleneoxy.
 10. A compound according to claim 1 wherein said B linking group is N-arylaminocarbonylalkyleneoxy.
 11. A compound according to claim 1 wherein said B linking group is N-alkylamino.
 12. A compound according to claim 1 wherein said B linking group is N-arylamino.
 13. A compound according to claim 1 wherein said B linking group is N-alkylaminoalkyleneoxy.
 14. A compound according to claim 1 wherein said B linking group is N-arylaminoalkyleneoxy.
 15. A compound according to claim 1 wherein said B linking group is oxyalkyleneoxy.
 16. A compound according to claim 1 wherein said B linking group is oxyaryleneoxy.
 17. A compound according to claim 1 wherein said B linking group is oxymethylene.
 18. A compound according to claim 1 wherein said B linking group is methyleneoxy.
 19. A compound according to claim 1 wherein said B linking group is oxymethyleneoxy.
 20. A compound according to claim 1 wherein said B linking group is oxyethyleneoxy.
 21. A compound according to claim 1 having the formula: ##STR9##
 22. A compound according to claim 1 having the formula: ##STR10##
 23. A compound according to claim 1 having the formula: ##STR11##
 24. A compound according to claim 1 having the formula: ##STR12##
 25. A compound according to claim 1 having the formula: ##STR13##
 26. A compound according to claim 1 having the formula: ##STR14##
 27. A compound according to claim 1 having the formula: ##STR15##
 28. A compound according to claim 1 having the formula: ##STR16##
 29. A compound according to claim 1 having the formula: ##STR17##
 30. A compound according to claim 1 having the formula: ##STR18##
 31. A compound according to claim 1 having the formula: ##STR19##
 32. A compound according to claim 1 having the formula: ##STR20##
 33. A compound according to claim 1 having the formula: ##STR21##
 34. A compound according to claim 1 having the formula: ##STR22##
 35. A compound according to claim 1 having the formula: ##STR23##
 36. A compound according to claim 1 having the formula: ##STR24##
 37. A compound according to claim 1 having the formula: ##STR25##
 38. A compound according to claim 1 having the formula: ##STR26##
 39. A compound according to claim 1 having the formula: ##STR27##
 40. A compound according to claim 1 having the formula: ##STR28##
 41. A compound according to claim 1 having the formula: ##STR29## 